Amino acrylates



Patented May 11, 1948 AMINO ACRYLATES Herbert I. Bernstein and Donald Long, Chicago, Ill., assignors to Quaker Chemical Products Corp., Conshohocken,

Pennsylvania No Drawing. Application September Serial No. 555,588

Pa., a corporation of 6 Claims. (Cl. 260-482) This invention relates to alpha amino esters, and more particularly relates to compounds of the type where R1 stands for an alkylidene group, preferably a methylene radical, R2 is any aliphatic group but generally is an alkyl radical, R3 and R4 stand for alkyl, aralkyl or aryl groups, or R3 and R4 together stand for an alkylene group, such as Methyl alpha-diethyl amino acrylate, ethyl alpha dipropyl amino ester of crotonic acid, and butyl alpha diethyl amino ester of beta ethyl acrylic acid, are examples of compounds coming under our invention.

These compounds are useful as textile adjuvants, as well as starting materials for the syn thesis of useful organic substances for example, pharmaceuticals.

The compounds of this invention may be made by the heat decomposition of alpha beta diamino esters, particularly of alpha beta diamino fatty acid esters of fatty acids having from two to six carbon atoms inclusive. Suitable compounds of this type include methyl di-ethyl-amino-propionate, ethyl di-dimethyl-amino-butyrate, various compounds shown in the examples and other compounds which will be apparent to those skilled in the art. Suitable temperatures and time of heating vary widely as will be apparent from the examples, but we prefer to effect the decomposition by heating the alpha beta diamino ester at above about 200 C. and not more than about 100 C. above its boiling point at atmospheric pressure. A heating time of between one to five hours gives satisfactory results.

A series of reactions illustrating the preparation of methyl alpha-diethy1 amino acrylate as carried out in Example I are given below:

The following examples further illustrate the invention:

EXAMPLE I Methyl a-diethylamino acrylate 378 parts of methyl alpha-chloroacrylate, 250 parts of benzene, 459 parts of diethylamine, and 10 parts of hydroquinone are mixed and refluxed for 8 hours. After filtering the precipitated amine hydrochloride, the filtrate is vacuum distilled. After removal of the benzene, 484 parts of a yellow oil, boilin point -105 C. at 4 mm. of pressure. Redistillation of this material yields 227 parts of a liquid consisting of methyl di-diethylamino propionate, boiling point 74 C. at 0.5 mm., n 1.4398,

69 parts of methyl didiethylamino propionate was decomposed by distilling it through a 12" Vigreux column. The bath temperature was kept at 220-245" C. for 1%, hrs., during which time 11.0 parts of diethyl amine formed and distilled over.

The bath temperature was then increased gradually to 280 C. and 53.0 parts of distillate collected, boiling point ISO- C., over an hour and a half. The 53.0 parts of liquid was distilled in vacuum, and the fraction boiling at 88-96 C. at 20 mm. was collected.

This iractionwas mm., a 1.4558-1A563. I

Exams 11 Methyl a-dlcthylamiho acrylateredlstilied to yield 10.0 partsv of methyl -diethylamino,acrylatc.40.2%.or the theoretical amount, boiling-point 80-91 C. at '20 v Q a tion of this oil for three hours at 180 0. yielded 115 parts or methyl di-diethylamino propionate was decomposed by distilling it throuch a 12" Vigreux column at a bath temperature or 215 C. Alter 18.1 parts of diethyl amine had been collected, the bath temperature was gradually increased to 280 C. over a 4% hr. period. 77.1 parts or distillate was collected. boilinfl point 110- 140" C., and a residue of 19.0 part8 remained undistilled.

The distillate was relractionated at mm. pressure to yield considerable low boiling material and 9.0 parts or methyl a-dlethyi amino acrylate, boiling point 89-96 11.5% yield. This result indicates that it is important not to run the decomposition reaction over too long a period. Higher yields are obtained when the decomposition reaction is run at a shorter period of time such as for 2 hours at 280 C.

Exnrrum Copolymerization of methyl a-dtethylmhlno acrylate and methyl methacrylate Mixtures of '15 parts of methyl methacrylate, parts of the amino acrylate, and 2 parts of t-butyl hydroperoxide could be polymerized to a soft, clear, red polymer by heating for a week at 105 C.

Mixtures of 90 parts of methyl methacrylate, 10 parts of amino acrylate, and 2 parts oit-butyl hydroperoxide polymerized to a hard, clear, red resin when heated 1 week at 105 C. Benzoyl peroxide gave a viscous, clear, red liquid under the same conditions.

Exurrts IV Methyl alpha-morpholinoacrylate 17.4 parts of morpholine is slowly added to 12.0 parts of methyl alpha-chloroacrylate in 8 parts of benzene containing 0.5 part of hydroquinone. After the initial heat of reaction has subsided, the mixture is refluxed for 22 hours. The 10.6 parts of morpholine hydrochloride formed is filtered ofl, washed with benzene, and dried to give a white solid, melting point 174 C., 86.6% yield. The filtrate is distilled in vacuo. After removal or the benzene, 12.0 parts of a light yellow distillate was obtained, boiling point 130-l50 C. at 0.5 mm. This liquid was then decomposed by heating for two hours at 180 C., producing methyl alpha-morpholinoacrylate.

Exmu V Methyl alpha-(N-mcthylaniliaol -acrylate cni=ooooorn N-CHI 21.4 parts benzene, 12.0 parts acrylate. and 0.5 part fluxed for 18 hours.

some 122424", moment-mun. hydrochloride.

Further distillation or the original reaction mixture'yielded a light yellow oil. Heat decomposithe methyl alpha-(N-methyl aniiino) acrylate. Exams VI Methyl alpha-dibenzylaminoacrylate Exsmrs VII Methyl alpha-distearylaminoacrylate 203 parts of distearylamine, 160 parts of henzene, 23.4 parts of methyl alpha-chloroacrylate,

and 5 parts of hydroquinone were mixed and heated to refluxing for 7 hours. 106 parts of distearylamine hydrochloride were removed by filtration. That thi was the hydrochloride was shown by the precipitation of silver chloride from a warm aqueous silver nitrate solution. The benzene was distilled from the filtrate in vacuo. The

residual solid was recrystallized from an alcohol- 7 ether solution and then heated for four hours at 200 C. to give methyl alpha-distearylaminoacrylate.

This application is a continuation in part of our copending application Serial No. 502,023, filed Sept. 11, 1943, now abandoned.

While there have been shown and described certain embodiments of the invention, it is to be understood that it is capable of many modifications. Changes, therefore, may be made without departing from the spirit and scope of the invention as described in the appended claims, in which it is the intention to claim all novelty inherent in the invention as broadly as possible, in view of the prior art.

We claim:

1. A new compound having the formula wherein R1 stands for a radical of the group consisting of CH2=, CHa-CH=, and

R2 is a lower alkyl radical, and X stands for a radical of the group consisting of CHr-CH: CHr-CH: Rs

-N\ CH1, O, and

CHr-Cfi: CHz-Ca Rt wherein R3 and R4 stand for radicals of the group consisting of an aikyl, phenyl and benzyi.

2. The method of preparing an alpha dialkyl 5 v 6 ate to a. temperature of between'approximately 200 0. and 280 0. for a period r between'ap- P sums PATENTS Y proximately 1 to 5 hours, removing the diethyl er Nlme Date amine formed during the heating by distillation 7 2 185, 44 co son Nov. 8. 1938 and separating from the resigue by distillation a 3 .13 1031 Graves Nov. 29,- 1938 fraction having a. boiling point oz 110 t 150 Y 2,211,152 Nicodemus et a1. Aug. 13; 1940 at substantially atmospheric pressure. 33 L54 Jacobson Feb. 16, 1943 f f 5 0mm mmmcns 5. As a new compound, a. lower alkyl ester of an 10 Sirius 91 Deuthem." vol. 59-13 pha diellwl amino acrylic acid. 9 DD- 1 v 6 Methyl alpha methyl m acrylate Marvel et aL: Jour. Am. Chem. 800., vol. 61

HERBERT I, BERNS'IEIN'.' 1989).pp- 7 I DONALD LQNQ. H Mcmwein et 9.1.: Jour. Am. Chem. 8012.," vol.

as (1941),;1.sins-4:217. REFERENCES-omen 3 I v, I The following references are of record In the tile 01' this patent: 

